Sodium salts of chlorinated c19-alpha-alkyldicarboxylic acids



' nated dicarboxylic acids.

in a solvent stable to chlorine.

effected in manner, the carbon structure of the di-' United States Patent 3,164,631 SODIUM SALTS 0F (JHLORINATED Cm-a-ALKYL DICARBOXYLIC ACIDS V Hans Feichtinger, Dinslahen, and Hans-Joachim Tomuschat, 0herhansen-Sterkrade-Nord, Germany, assignors to Ruhrchemie Alrtiengesellschatt, Oherhausen-Holten, Germany, a German corporation No Drawing. Filed Sept. 2, 1959, Ser. No. 837,590 Claims priority, application Germany Sept. 6, 1958 1 Claim. (Cl. 260-514) This invention relates to an improved process for the production of chlorinated dicarboxylic acids.

An object of this invention is the provision of anefiicient and economical process for the production of chlori- Another object of this invention is to provide a process which is adapted to be employed in' the preparation of chlorinated dicarboxylic acids, which process comprisesreacting a dicarbowlic acid with chlorine in the presence of a solvent inert with respect to the chlorine. y

Various other objects and advantages will be apparent as the nature of the invention is more fully disclosed;

Chlorinated aliphatic dicarboxylic acids have previously been prepared by chlorination in the absence o fany solvent .of their corresponding dichlorides, dinitriles or dimethyl esters. Thechlorinated dichlorides, dinitriles or dimethyl esters are in turn reacted in the conventional manner to produce the desired dicarboxylic acids. The

chlorinated dicarboxylic acids can also be prepared by addition of chlorine or hydrogen chloride to the olefinic free bonds present in the starting dicar-.

or acetylenic boxylic acid.

It has now been found that straight-chain, branchedchain and cycloaliphatic free dicarboxylic acids may easily be" chlorinated if the same are dissolved or suspended When the chlorination is acid-(4,8), as well as both the solid and liquid terpane-di-;

carboxylicacids, which are prepared according to British patent specification No. 766,913. C -a-alkyldicarboxylic acid mixtures of the general formula t O nooo-gomn-trnoobn such 'as are obtained by hydroformylation of technical oleic acid, hydrogenation of the hydroformylation prod- 3,164,631 Patented Jan. 5, 1965 net followed by alkali fusion, which are prepared according to French patent specification No. 1,189,133, may

easily be chlorinated in accordance with theiinvention.

The c -u-alkyldicarboxylic acid is most conveniently chlorinated employing carbontetrachlorid as solvent and by passing in gaseous chlorine while irradiating with ultra violet light. When dicarboxylic acids are to be chlorinated, which are only difi'iculty. soluble or substantially insoluble in the solvent, then the chlorination is carried out with the acid suspended in the solvent.

Chlorination in accordance with the invention comprises the treatment in solvents stable, i.e. inert to chlorine or di cycloaliphatic hydrocarbon radical.

carboxylic acids, with gaseous chlorine without or in the presence of catalysts at normal or elevated temperatures. The method according to the invention may be carried out employing dicarboxylic acids having a sufliciently large carbon structure to take up at the time the amount of chlorine desired. The chlorination according to the invention is especially adapted for the chlorination of 'dicarboxylic acids of the type. HOOC-ACOOH, where in .A is a straight-chain or branched-chain aliphatic or Thus, for example,

. dicarboxylic acids of the general formula noocj-"(Cnn -coon may be. employed as starting materials, wherein n may have a value of at least 4. These acids are homologues of the non-branched a,w-dicarboxylic. acids having 6 or i more carbon atoms in their molecules. Any branchedchain dicarboxylic acid having 6or more carbonatoms in its molecule'may be chlorinated according to the invention; acid, tetradecylglutaric acid, a-propyl-adipic acid, wmethyl-pentadecandioic acid and dicarboxylic acids having similar structures. 'Cyclo'aliphatic dicarboxylic acids of the following general formula may also be chlorinated in accordancewith the invention:

wherein m represents the number of'carb on atoms contained in the ring system and Z represents the number of rings present in the molecule, whereby Z is a whole number which must at least have the value of 1. R represents the same or different alkyl radicals present in the ring, their number amounting to p, whereby p represents a Whole number or Zero and n and lrepresent Whole numbers but may also have the value of zero.

w Included within the above general formula are, for

example, tricyclodecane-(5,2,l,0 )-dicarboxylic acid- (4,8), d,a-hexamethylene sebacic acid, cyclohexane-diacetic acid-(1,2), terpanedicarboxylic acidsand dicarboxylic acids of similar structure. The acids maybe chlorinated as single acids or as mixtures of these acids.

Chlorination according to the invention is efiected after dissolving or suspending the free dicarboxylic acids in v solvent stable to c'hlorineand preferably in carbon tetra- Such acids are exemplified by decylmalonio chloride by passing in gaseous chlorine at normal or elevated temperatures. The chlorination may be carried out while irradiating with actinic light or by heating the solution saturated with chlorine in the presence of a catalyst effective as transmitter of halogen, such asiodine.

The chlorine is taken up by substitution of the hydrogen available in the hydrocarbon portion of the dicarboxylic acid treated and with the evolution of an equivalent amount of hydrogen chloride. In this way, both of the carboxylic acid groups remain unchanged. The chlorine substitution, efiected in the presence of solvents stable to chlorine, takes place Without outside heat addition and with considerable evolution of heat. The reaction may be stopped at any time after the desired chlorine content has been obtained.

, Following evaporation of the solvent, the chlorinated v face-activcmaterials and thus of considerable interest to the pharmaceutical, perfume and soap industries.

From the dicarboxylic acids, chlorinated in accordance with the invention, the corresponding soaps may be producedby conversionwith the equivalent amount 7 of an inorganic or organic base. These soaps exhibit exof. the molecule, are known as foaming agents.

cellent foaming qualities This fact could neitherfbe foreseen nor have been derived from the structure of the soaps. Compounds With long hydrophobic radicals and two hydrophilic' groups, the one of them arranged in thecenter and the other arranged at the end portions This is confirmed, for instance, by the properties of th e alkaline salts of a C -oc-alkyldicarboxylic1acid mixture However, when the dicarboxylic' acid mixture is chlorinated according to the disclosure, water-soluble soaps are ob-' tained which show remarkable foaming properties, and this also in theacid'range. The foaming capacity of the non-chlorinated soaps is lowered considerably by any change from' the alkaline range to the neutral point of the solution involved and is-extrernely low in the weak acid range. It is known that the foaming consistency and foaming de'nsity, which are both already low in aikaline solutions, will even'be lessened in conditions where acidification has taken place.

Therefore it is to be considered most surprising that alkaline salts of the corresponding chlorinated acids in aqueous solution 'show a very high foaming capacity; It is optimum even in the acid-range. densityv surpasses that of thenon-chlorinated acids in a soapof this type, adjusted for exampleto the pH value of 6.65, after hours had a pH value of 6.60 and after 100 hours a pH value of 6.50. Therefore, these solutions represent valuable auxiliary materials for use in the textile and detergent industries and may also serve admirably for the cleansing and regeneration of.

metallic salts produced therefrom in reducing the inflammability of the materials impregnated therewith is additionally most surprising; This property may be clearly demonstrated, employing a filter paper strip impregnated from mid to the end point thereof which, when ignited at-the non-impregnated end, commenced to burn away, slowly until the point or impregnation was reached, at which point the flame was extinguished. v Y

The following examples illustrate in greater particularity the method of preparing the various chlorinated dicarboxylic acids. It will be understood that these e:- amplcs are given for purposes of illustrating preferred processes andarenot to be construed as limiting theinvention to the processes described therein.

-Glass flask, provided with agitator, reflux cooler and gas inlet pipe. The chlorination was effected bypassing in gaseous chlorine without heat addition, but under agitation and irradiation with a 500 watt ultra-violetlight,

until yellowish-green chlorine was clearly seen in the cooler. The solvent .waslthe n distilled'in vacuum, and

The foaming 1 thev alkaline range and'is still iconsiderably elevated in I the acid range. A number of soaps, as produced from dicarboxylic acids chlorinated according to the invention,

show good foaming. capacities in organic solvents, as

The improvement of the foaming properties of a noni chlorinated acid with the corresponding chlorinated acid is clearly shown in-Example -13 (infra). This type of finally the residue was recovered by distillation in high vacuum on a water bath at C. The chlorinated product was a White, brittle, amorphous'powder having a softening point of about 100 C. The product still conpolychloro-nonane-dicarboxylic acid containing 19 gram atoms of chlorine per molecule and'having an acid number of 114 (calculated, 114.2). a

EXAMPLE 2 -20 g-. tetradecylglutaric acidwere dissolved under heat in 200 cm. carbontetrachloride and then chlorinated without further heat addition substantially. as outlined in V Example 1. The chlorination product was a white, brittle, for example in hydrocarbons or chlorinated hydrocarbonsv foaming acid solutionrformed from alkaline salts of dicarboxylic j acids is completely exceptional, since, as is ,Well known, the neutral'saltof a strong base with a weak acid'shows an alkaline reaction in aqueous solution. 1

The solutions as prepared from-thewsalts of dicarboxylic acids chlorinated according to the invention,

change their pH value only slightly at room temperature, and that over several days. A 5% aqueous' 'solution of amorphous powder with a softening point of about C.,

still containing'carbon tetrachloride. Yield was 68 g. dry" and having an acid number of 102 (calculated, 10.7).

EXAMPLE 3 30 g. tricyclodecane-(521,0 3) -dicarboxylic acid-(4,8)

product was a White, brittle, amorphous powder with a 100 g. of an oily Cw-ot-filkYldiOfiIbOXj/HC acid mixture, as prepared by hydroformylation of oleic acid, hydrogenation and subsequent alkaline fusion, were dissolved in 500 com. carbon tetrachloride and chlorinated by the procedure as outlined in Example 1. Within an hours time, liters of chlorine gas were passed into the solution. Without additional heating the temperature of the reaction mix ture was raised to the boiling point of the solvent. Subsequently, the solvent was distilled off and the remaining solvent was removed. in high vacuum on a water bath of 60 C. In this way, 119 g. of residue was recovered as a yellowish, clear, oily liquid having a chlorine content of 16.4%. The final product consisted of a polychloro c -a-alkyldicarboxylic acid mixture containing 1.9 gram atoms of chlorine per molecule and having an acid number of 287 (calculated, 287.7).

EXAMPLE 5 EXAMPLE 6 A solution of 100 gar the c -a-alkyldicarboxylic'acid mixture, employed in Example l, in 500 com. carbon tetrachloride wastreated with 82 liters of chlorine gas over a period of 5.5 hours under conditions substantially as outlined above and then worked up in the same way. The residue was a white, brittle, amorphous powder having a softening point of about 70 C. The powder still contained carbon tetrachloride, which was removed asoutlined in Example 1. Yield of dry product was 214 g., showing a chlorine content of 54.3%]. The final product consisted of polychloro-C a-alkyldicarboxylic acid mixture containing 10.7 gram atoms of chlorine per molecule and having an. acid number of 161 (calculated, 161.2).

EXAMPLE 7 V Chlorine gas waspassed into a solution of 100 g. of a c -a-alkyldicarboxylic acid mixture .in 500 ccm. carbon tetrachloride, as employed 'in Example 4, for such a period of time and under such conditions as outlined in[;Exainple 1 untilyellowish green chlorinewas clearlyshown in the reflux cooler. The reaction mixture was worked' up by.

V distillation. The chlorination product wasa white, brittle,

amorphouspowder with a softening point of about 120 C.' It still contained carbon tetrachloride which" was removed by the procedure described in Example 1. Yield of dry substance was 268 g. showing a chlorine content of 64.0%. The final product consisted of'polychloro- C -a-alkyldicarboxylic acid mixture containing 15.7 gram atoms of chlorine per molecule and having an acid number of 129 (calculated, 129.2).

EXAMPLE 8 V 100 g. of a C -d-alkyldicarboxylic acid mixture, em-.- ployed according to Example 4, were chlorinated underconditions as outlined in Example 7, differing only in that a quartz vessel was used. The while, brittle, amorphous powder obtained showed asofte'ning point of 125 C. It still contained carbon tetrachloride which was removed according to Example 1. Yield of dry substance was 286 g., showing a chlorine content of 66.6%. The final product consisted of a polychloro-C .-a-alkyldicarboxylic acid mixture containing 175 gram atoms of chlorine per molecule and having an acid number of 120 (calculated, 120.5).

EXAMPLE 9 Following the addition of 150 mg. iodine at room temperature, a solution of 100 g. C-chlorinated C -walkyldicarboxylic acid mixture obtained according to Example 7 in 700 com. carbon tetrachloride was saturated with chlorine in a closed fusion tube for 8 hours at 120 C. After cooling, the solution was again saturated with chlorine gas, the hydrogen chloride gas formed was driven off and the same treatment repeated at135 C., 150 0., 160 C. and 170 C. The solution obtained was then subjected to a post-chlorination at normal pressure, employing ultra-violet radiation and worked up according to Example 1. Yield was 117 g. of a product having a chlorine content of 69.4%. The final product consisted of a 'polychloro-C u alkyldicarboxylic acid mixture coritain- EXAMPLE 10 100 g. of the C-chlorinated C -a-alkyldicarboxylic acid mixture, as obtained according to Example 7, were dissolved in 700'ccm. benzene and neutralizedwith an approximate l-N solution of sodium hydroxide in met h* anol. After evaporation of the solvent and drying of the residue, employing high 'vacuum, the disodium salt of the C-chlorinated Ci -a alkyldicarboxylic acid mixture was recovered as a solid, hard substance having a melting pointofbetween 165 .and 172 C. and containing 61.1% chlorine.

EXAMPLE 11 ccni. (V each of a 1% aqueous solution of the disodium salt obtained according to Example 12 were adjusted to pH values of 8.5, 8.0, 7.5, 7.0, 6.5, 6.0 and 5.5

' and brought to the foaming state at 20 C. in a 250 ccm.

measuringflask by uniform agitation for /2 minute of a perforated plate and the'respective solvent (V resp.

V and foaming volume (V resp. V checked in values of cm. after 1 and after 30 minutes' On the basis of these values, the foaming numbers were calculated after 1 (S and 30 minutes (S the foaming consistency (S and the foaming density after l (S and after 30 minutes (S Foaming number: i

A similar test was conducted, employing the disodium soap of the non-chlorinated acid, the results being listed' in the following table, as medium values'each represent, ing 10 determinations. i

arcaear Table I of two other washing substances] pH Szi Szan SDi SD30 Sn 8. 5 480 391 0. 193 0. 028 0. 815 8. 470 381 0. 195 0. 030 0. 810 The (ii-sodium salt of a poly- 7. 478 380 0. 198 0. 030 0.798 ch1oro-Ciu-walkyldioar 7.0 495 405 0. 2'10 0.031 0.818 boxylic acid mixture con- 6.5 495 420 7 0.200 0.035 0.841 taining 157 gram atoms of 6. 0 483 410 0.201 0.055 0.852 chlorine per molecule. 5. 5 420 357 0.211 0. 080 0.840

8. 5 450 320 0. 190 0. 001 0. 711 8.0 463 331 0.190 0.001 0.713 The di-sodium salt of a C19- 7. 5 471 342 0.190 0.001 0.720 a-alkyldicarboxylic acid 7. 0 463 336 i 0.192 0.002 0.720 mixture without chlorine. 6; 5 400 255 0. 200 0. 003 0. 630

8. 5 462 352 0. 195 a 0.010 0.781 8. 0 452 360 0. 195 0.010 0.780 7. 5 452 359 0.195 0. 010 0.780 N-oleyl-aminobutanesul- 7. 0 443 349 0. 195 0.010 0. 799 tonic sodium-salt (Trade 6. 5 438 342 0.196 0.010 0.799 Name Ercepon) 6. 0 433 337 0. 197 0. 010 0. 798 5. 5 430 332 0. 197 O. 010 0. 798

8.5 410 263 0.207 0.009" 0.641 8.0 .410 270 0.206 0.008 0. 657 7.5 410 276 0.205 0.008 0.671 N-mcthyl-a-olein-ainino- 7.0 410, 281 0.204 0.008 0.681 ethane-sulfouio-sodium- 6. 5 411 288 0.203 0.008 0.089 salt (Trade Name Ho'st- 0. 0 412 288 0. 202 0. 008 0. 092 apon). 5.5 413 289 0 202 0.008 0. 092

EXAMPLE 12 in a vacuum desiccator. .The blue copper salt of the polychloro-Ci -a-alkyldicarboxylic acid mixture showed a melting range of 209+214 C. and a chlorine content According to-the procedure described in Examole' 12,

using aqueous Zinc chloride solution, the white zinc salt of a polychloro- C 9-o -alkyldicarboxylic'acidmixture was obtained.. The melting range was 170-174 C., and the 10.0 grams of acid were suspended in 650 com.

carbon tetrachloride and chlorinated as described above while being irradiated With-'actinic light. After evapj aration of the solvent, 183 grams (calculated, 181 grams) 5 of polychloradipic acid containing 3.4 gram atoms of carbon tetrachloride and chlorinated in the manner de- .;;Fr;om the aqueous solution of'thedisodium salt of the scribed above. After having driven ofi'the solvent, 232

grams (calculated, 228.5) of polychloroterpanedicarboxyl ic' acid containing 8.5 gram atoms of chlorine per a molecule were obtained as a white substance having a softening point of 92 C.,.- achlorine content of 57.9% and an acid number ot 206 (calculated, 215.0),

. EXAMPLE 17 100 grams or" liquid terpanedicarboxylic-acid having the empirical formula (3 11 were dissolved in 600 com. of a carbon tetrachloride and chlorinated with gaseous chlorine in the manner described aboveo After evapora tion' of the solvent, 260 grams (calculated, 247.5) of polychlor'oterpanedicarboxylic acid containing 9.8 gram atoms of chlorine per molecule were obtained asa white substance having -a softening point'of 78, C., a chlorine con-- tent of 61.4%, and an acid number 05188 (calculate-d,

. .EXAMPLEY 1 8 :20 granisyof polycliloro-C -;t alkyldicarboxylic 'acid I mixture containing 15.7 gram atoms of chlorine per molchlorine per moleculefwere obtained as'ayellowish solid substance having a softening pointof. about 120 C; a

chlorine content of 46.0% and (calculated, 424.5 f

j EXAMPLE 1 5 20 grams of'cetylmalonic acid were suspended in 200 com. of carbon tetrachlorideand treated with gaseous chlorine'while irradiatingwith the light of a mercury an acid'n umber of 423 .vapor lamp. -After havingdriven oil the solvent, 63

softening point of 85 C., a chlorine content of 69.2%, and an acid number of. 103 (calculated,v 109.5).

EXAMPLE 16'.

i 162 gram atoms of'chlorine per molecule and having a f gramsof, solid terpanedicarboxylic acid'ha'ving the I empirical-"formula G i-I 0; were suspended in 600 com.

cooling, the solution Was fagain saturated'wit ecule (see Example 7) were dissolved in 140 com. carbon tetrachloride, mixed with 30 milligrams of iodine, and the solution which was'saturated with gaseous chlorine was heated for ohours at ".C.'in ase aled-tube. Upon I gaseous chlorine ,llydrogen chloride formed thereby was driven ofi aud t he same'oper ation carried out at 150, 160, and 17o -c..

Following'this, ;the product was worked up, resulting in 19.6 grams (calculated, 20.4 grams) poly ch10!0-Cig o;alkyld1QaIbQX 11C acid I mixture containing chlorine content of 64.8%,"a softening point of 122 C.

. and an acid number of .125-,7 (calculated, 126.6).- 7

The chlorination ofiother/dicarboxylic acids accord-' dition of heat in aflask providedwithagitator, reflux cooler and inlet tube for chlorine. by passing in gaseous chlorine'under agitati on and irradiation with a 500 watt ultraviolet lampof the Quarzlampen G.m.b.1-l., Hanan (Main), Germany. In'order to assure completeichlori- 9 nation, chlorine gas was passed in for such length of time that yellowish green chlorine showed up in the cooler. In case a definite stage of chlorination was to be reached, the chlorine volume to be passed in was then'checked by dosing, using a flowmeter. After the chlorination Was completed, the solvent was first distilled oil in vacuum and the chlorination product was finally dried in high vacuum, using a Water bath at 60 C.

The amounts of chlorine taken up in the chlorination of some dicarboxylic acids according to the invention are shown in the following table:

Table II The chlorinated dicarboxylic acids, as prepared according to the invention, represent oily or high-viscous substances when small amounts of chlorine are taken up. Solids are obtained when large amounts of chlorine are taken up. This fact is shown in the following table,

specific with respect to the chlorination products of a C -oc-alkyldicarboxylic acid mixture:

Table III Product or, pcr- Acid 01, per Softcning No. Condition cent number mol point at;

about- Yellow, transparent, 13. 9 289 1. 6

or Yellow, transparent, 38.9 193.8 6.5

viscous. Yellow, transparent, 43. 3 183. 8 7. 6

extremely high-viscous. 4 White, amorphous, 52.6 167.2 10.0 C.

brittle, containing C014. 5 After drying in big 59.0 146.1 12.8 0.

Vacuum at 140 C. 6 Slightly yellowish--. 62.6 134.9 14.6 C.

We claim:

A foam-improving agent consisting essentially of a water-soluble sodium salt of-a chlorinated C -u-alky1- dicarboxylic acid prepared by reacting a solution of a C -u-alkyldicarboxylic acid with chlorine in carbon tetrachloride as solvent, recovering the chlorinated dicarboxylic acid thereby formed and saponifying said chlorinated dicarboxylic acid With sodium hydroxide to produce the corresponding sodium salt.

References Cited in the file of this patent UNITED STATES PATENTS 

